CN108735953A - A kind of SiO2- PS nucleocapsid ceramic-coated separators and its preparation method and application - Google Patents
A kind of SiO2- PS nucleocapsid ceramic-coated separators and its preparation method and application Download PDFInfo
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- CN108735953A CN108735953A CN201810689956.5A CN201810689956A CN108735953A CN 108735953 A CN108735953 A CN 108735953A CN 201810689956 A CN201810689956 A CN 201810689956A CN 108735953 A CN108735953 A CN 108735953A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/463—Separators, membranes or diaphragms characterised by their shape
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The present invention relates to lithium ion battery separator production technical fields, and in particular to a kind of SiO2- PS nucleocapsid ceramic diaphragm coatings, by dispersed nano SiO made from St ber methods2Particle in-situ grafting gamma-methyl allyl acyloxypropyl trimethoxysilane (MPS) is modified, and SiO is modified to dispersed nano using polyvinylpyrrolidone ethanol solution and styrene-azodiisobutyronitrile mixed liquor2Particle is coated with, and the nucleocapsid in conjunction with effect stability, the SiO of preparation are formed2- PS nucleocapsid ceramic diaphragm coating slurries, nucleocapsid SiO2The favorable dispersibility of-PS composite particles, it can be dispersed in coating slurry system without generating excessively agglutination, after polyolefin porous separator, the coating for not hindering polyolefin porous separator hole can be formed, and and the combination of polyolefin porous separator works well, and film integrally has good mechanical performance；Diaphragm has stable film form at high operating temperatures, effectively prevents caused by high temperature while the thermal contraction phenomenon of diaphragm, the SiO of stratum nucleare2For particle under the coating of glassy polymers, there is a phenomenon where ceramic powders to fall off, blocks diaphragm duct improves the safety of lithium ion battery to improve the heat resistance and stability of lithium ion battery separator.
Description
Technical field
The present invention relates to lithium ion battery separator production technical fields, and in particular to a kind of SiO2- PS nucleocapsid ceramics
The preparation method and applications of diaphragm coating and the diaphragm coating.
Background technology
Lithium ion battery is widely used in portable equipment field, and the electric vehicle for being also considered as most application prospect is dynamic
Power battery system, but the operating mode of its existing system, especially as electric vehicle electrical source of power when, technically still
There are certain security risks.In diaphragm type lithium ion battery, positive and negative pole material is prevented to be in direct contact by diaphragm, to avoid
Cause battery short circuit, be referred to as the third pole of lithium ion battery, is the big key for restricting lithium ion battery safety in utilization
Factor.Currently, most of commercialized liquid lithium ionic cell selects microporous polyolefin film as diaphragm, though it is with suitable
The advantages that aperture, the chemical property of stabilization, enough mechanical strengths, but due to poor dimensional stability at high temperature, be easy to shrink
Even melt rupture of membranes, cause internal short-circuit of battery, may cause battery that thermal runaway and then explosion on fire occurs.In addition, nonpolar
Polyalkene diaphragm have hydrophobic surface and lower surface energy, compatibility is poor between leading to remaining polarity electrolyte.
It uses various physics and chemical method to diagram modification at present, heat safe inorganic nano is coated in membrane surface
Grain is a kind of easy method that can effectively solve the above problems to enhance thermal dimensional stability and wettability.Common pottery
Porcelain particle has Al2O3、SiO2、CaCO3、BaSO3, MMT and TiO2Deng.Ceramic coating layer plays crucial work to the performance of ceramic diaphragm
With, and ceramic powder is the key components of ceramic coating, the experimental results all show that material property is formed with it, tied
The factors such as structure, pattern, grain size are closely related.Microcosmic ceramic powder property will have a direct impact on the ceramic coating spy of macroscopic view as a result,
Property so ceramic diaphragm performance is had an impact.Sang-Youang Lee seminars using infusion process be prepared for it is a series of containing
Variety classes bond and the composite diaphragm of inorganic particle, effectively improve the thermal stability and chemical property of diaphragm.Cao Chaoxia
Deng using PE diaphragms as coated substrate Kynoar（PVDF）With nanometer Al2O3Ceramic Composite diaphragm is prepared, ceramic coating modification carries
The capacity retention ratio of the high imbibition ability of diaphragm, thermal stability and battery.Luan etc. using teos hydrolysis reaction and
PVDF makees binder and is prepared for SiO in PP membrane surfaces deposition2Composite coating.Application No. is the hairs of CN 201410445356.6
Bright patent discloses a kind of diaphragm, the diaphragm be by coated in membrane surface ceramic material layer and be coated in ceramic layer outer surface
PVDF Polymer Tie-layers composition, improve the heat resistance of diaphragm, but coat the ventilative loss of diaphragm relative to former film
It is larger, the conduction of lithium ion is hindered, the internal resistance of lithium battery is increased；Complex procedures are coated, production efficiency is caused to decline, and
Thickness and weight increase, and are unfavorable for the lightweight of product.In addition, above-mentioned Ceramic Composite diaphragm still have in actual application it is all
More problems demands solve, and are concentrated mainly on following three points：(1) ceramic powder, which falls off, causes diaphragm duct to block；(2) ceramic powder
The dispersion of body is uneven；（3）Under 135-150 DEG C of hot conditions, hot closed pore performance is poor.
Invention content
The primary purpose of the present invention is that providing a kind of SiO2The preparation method of-PS nucleocapsid ceramic-coated separators,
Form the SiO of nucleocapsid2- PS particles are can be uniformly dispersed in diaphragm coating slurry；The SiO that the above method is prepared2-PS
Nucleocapsid ceramic-coated separator, finished battery diaphragm does not occur ceramic powder and falls off, blocks the phenomenon that diaphragm duct, and has
Hot closed pore performance under standby hot conditions, can have both chemical property and security performance, be suitable for answering as diaphragm simultaneously
For in all kinds of lithium batteries.
To achieve the above object, the present invention is implemented using following technological means：
A kind of SiO2The preparation method of-PS nucleocapsid ceramic-coated separators comprising following steps：
（1）Dispersed nano SiO2The preparation of particle：Concentrated ammonia liquor, ethanol solution and ethyl orthosilicate are mixed simultaneously, with St
At room temperature, envelope bottleneck is reacted and is centrifuged after stirring 18-24h ber methods, the dispersed nano SiO that will be obtained2Particle preserves
In ethanol solution, dispersed nano SiO is formed2Particle dispersion is for use；
（2）Dispersed nano SiO2The modification of particle：With dispersed nano SiO2The ratio of particle and deionized water 0.85-1mg/mL
Example, by dispersed nano SiO2Particle dispersion is added in the deionized water in four-hole boiling flask, after few drops of ammonium hydroxide are added dropwise, is added
Gamma-methyl allyl acyloxypropyl trimethoxysilane ethanol solution, and under inert gas protection by four-hole boiling flask in 50-60 DEG C
It is centrifuged after insulation reaction 18-30h, and dispersed nano obtained is modified SiO2Particle is stored in ethanol solution, is formed
Dispersed nano is modified SiO2Particle dispersion is for use；
（3）Monodisperse nucleocapsid SiO2The preparation of-PS composite particles：Dispersed nano is modified SiO2Particle dispersion is dispersed in
In polyvinylpyrrolidone ethanol solution in four-hole boiling flask, and two isobutyl of styrene-azo is added dropwise under the conditions of nitrogen protection
Nitrile mixed liquor simultaneously continues after stirring 2-3h, is kept stirring and is heated under 65-70 DEG C of state centrifugation point after insulation reaction 12-18h
From, and by obtained monodisperse nucleocapsid SiO2- PS composite particles are stored in ethanol solution；
（4）SiO2The preparation of-PS nucleocapsid ceramic diaphragm coating slurries：By monodisperse nucleocapsid SiO2- PS composite particles use
After toluene washing, centrifuges and take monodisperse nucleocapsid SiO2- PS composite particles, aqueous adhesive, solvent are with 70-100:1~5:500~
1000 weight ratio mixing makes each component is fully dispersed to be formed uniformly homogeneous mixed serum, and slurries obtain after crossing 200 mesh sieve
Obtain SiO2- PS nucleocapsid ceramic diaphragm coating slurries；
（5）SiO2It is prepared by-PS nucleocapsid ceramic-coated separators：Using automatic coating machine by SiO2- PS nucleocapsids ceramics every
After membrane coat slurries single or double is coated on polyolefin porous separator, 12-18h is dried with 55-65 DEG C of vacuum drying oven, is made
SiO2- PS nucleocapsid ceramic-coated separators.
In above-mentioned technical proposal, the step（1）In, the concentrated ammonia liquor, ethanol solution and ethyl orthosilicate volume ratio
It is 1 ~ 2:5~15:1~2；After centrifugation, sieve takes grain size in 50 nm and dispersed nano SiO below2Particle is stored in ethyl alcohol
It is for use in solution.
In above-mentioned technical proposal, the step（2）In, the gamma-methyl allyl acyloxypropyl trimethoxysilane ethyl alcohol
Solution concentration is 0.02-0.05mg/mL；Deionized water:The body of gamma-methyl allyl acyloxypropyl trimethoxysilane ethanol solution
Product is than being 2-5:1.
In above-mentioned technical proposal, the step（3）In, the polyvinylpyrrolidone ethanol solution is polyvinylpyrrolidine
The ethanol solution of ketone K30 and 50%-75% are made with 0.2-0.5mg/mL allotments, the styrene-azodiisobutyronitrile mixing
Liquid is dissolved in styrene allotment with 0.02-0.05mg/mL concentration for azodiisobutyronitrile and is made, and dispersed nano is modified SiO2?
Grain dispersion liquid：The total volume ratio of polyvinylpyrrolidone ethanol solution, styrene-azodiisobutyronitrile mixed liquor is 2-3:1.
In above-mentioned technical proposal, the step（4）In, by monodisperse nucleocapsid SiO2- PS composite particles are abundant using toluene
After being centrifuged at a high speed after washing, monodisperse nucleocapsid SiO is fully washed using ethyl alcohol2- PS composite particles, then centrifuge, and
By monodisperse nucleocapsid SiO2- PS composite particles, aqueous adhesive, solvent are with 70-100:1~5:500 ~ 1000 weight ratio mixing
It uses ultrasonic disperse to be carried out at the same time 2-3h with mechanical agitation afterwards, makes each component is fully dispersed to be formed uniformly homogeneous mixing slurry
Liquid.
Further, the aqueous binders select the compound of butadiene-styrene rubber and carboxymethyl cellulose, polyvinyl alcohol poly-
Any one in acrylate, gelatin, sodium styrene sulfonate, acrylonitrile multiple copolymer, dextrin, poly- lithium -4- styrene etc.
Or compounding.
Further, the solvent is ethanol water, water/n,N-dimethylacetamide mixed solvent etc., and proportioning can join
The requirement for examining final products is adjusted.
In above-mentioned technical proposal, the step（5）In, the polyolefin porous separator is the PP of porosity 30%-60%
Film, PP and PE multilayer complex films, passes through any one in the non-woven polyolefin of spin processes preparation, the polyolefin at PE films
The thicknesses of layers of porous septum is 10 ~ 20 μ 0, the SiO per side2- PS nucleocapsid ceramic diaphragm coating slurry coating layer thicknesses 2-5
μ-。
The SiO prepared using the above method2- PS nucleocapsids ceramic-coated separator and the SiO2- PS nucleocapsids are made pottery
Application of the porcelain coated separator in lithium ion battery separator is also within protection scope of the present invention.
The present invention has following usefulness：
（1）Patent of the present invention on the basis of traditional ceramics diaphragm effectively can inhibit thermal contraction, from the structure of ceramic powder and
Two aspects of ingredient are started with, it is designed and controlled well.By to dispersed nano SiO made from St ber methods2
Particle in-situ grafting gamma-methyl allyl acyloxypropyl trimethoxysilane (MPS) is modified, molten in polyvinylpyrrolidone ethyl alcohol
Styrene monomer is modified SiO under initiator azodiisobutyronitrile effect to dispersed nano in liquid dispersion2Particle carries out
Embedding, the nucleocapsid formed in conjunction with effect stability make dispersed nano be modified especially with the reactive mode of dropwise addition-stirring
SiO2After particle is fully embedded, the insulation reaction at suitable temperature makes SiO2- PS nucleocapsids form rock-steady structure, and anti-
Should after pass through toluene and clean nucleocapsid SiO2The free PS on-PS composite particles surface and other impurity, the SiO then prepared2-
PS nucleocapsid ceramic diaphragm coating slurries, nucleocapsid SiO2The favorable dispersibility of-PS composite particles can be realized effectively evenly dispersed
In coating slurry system ceramic coated is efficiently solved after being coated on polyolefin porous separator without generating excessively agglutination
Negative effect to polyolefin porous separator porosity, and work well with the combination of polyolefin porous separator, film integrally has
Standby good mechanical performance；
（2）Ceramic coating produced by the present invention, which combines ceramic diaphragm at high temperature, can remain dimensionally-stable and gelatin polymer electricity
The advantages of mass-energy stablizes electrolyte is solved, there is good heat resistance, SiO2The enough thermal contractions for effectively inhibiting diaphragm of nuclear energy, improve electricity
Pond safety.PS shells form after electrolyte activates and absorb and keep Electrolyte Gel state substance, have higher conductance
Rate strengthens the interaction between diaphragm and electrolyte, improves the compatibility of diaphragm and electrolyte；Another PS shells 80 DEG C with
On start to glassy state convert, the polymer insulation layer of formation has the function of hot closed pore, when temperature continues to rise to 135 ~ 150 DEG C
When the high temperature range of range, the part AIBN of shell is released, and can induce part PS, vistanex in molecular level
In-situ polymerization forms glassy state condensate under high temperature, further increases the hot closed pore performance under the condition of high temperature；The SiO of stratum nucleare2?
Grain makes the thermal dimensional stability of diaphragm enhance, the film form for maintaining diaphragm to stablize at high operating temperatures, effectively prevents to make because of high temperature
At diaphragm thermal contraction phenomenon while, the SiO of stratum nucleare2Under the coating of glassy polymers ceramic powder does not occur for particle
It falls off, block the phenomenon that diaphragm duct, to improve the heat resistance and stability of lithium ion battery separator, improve lithium ion
The safety of battery.
Description of the drawings
Fig. 1 is the SEM figures of the embodiment of the present invention 3
Specific implementation mode
The content further illustrated the present invention with reference to the accompanying drawings of the specification with specific embodiment, but should not be construed as to this
The limitation of invention.Unless otherwise specified, the conventional hand that technological means used in embodiment is well known to those skilled in the art
Section.Unless stated otherwise, the present invention uses reagent, method and apparatus is the art conventional reagent, methods and apparatus.
In following test case, certain the commercially available ceramic coated battery diaphragm of comparative example 1, embodiment 1,2,3,4 is according to following realities
Apply step preparation.In the performance test of following each embodiments and comparative example final products, with reference to DB44/T 1152-2013《Lithium
Ion battery polyethylene diagrams》, and each embodiment and comparative example carry out five parallel tests and are averaged.
Embodiment 1
（1）Dispersed nano SiO2The preparation of particle：15mL concentrated ammonia liquors, 120mL ethanol solutions and 12mL ethyl orthosilicates is same
When mix, at room temperature with St ber methods, envelope bottleneck react and is centrifuged after carrying out magnetic agitation 18-24h, and sieve take grain size
In 50 nm and dispersed nano SiO below2Particle is stored in ethanol solution, forms dispersed nano SiO2Particle dispersion waits for
With；
（2）Dispersed nano SiO2The modification of particle：With dispersed nano SiO2The ratio of particle and deionized water 0.85mg/mL
Example, by dispersed nano SiO2Particle dispersion is added in the deionized water in four-hole boiling flask, by 0.5mg γ-metering system
Monomethacryloxypropyl trimethoxy silane is mixed with 20mL ethyl alcohol, will prepare gamma-methyl allyl acyloxypropyl trimethoxysilane ethyl alcohol
After solution is added into four-hole boiling flask and 5-10 drop ammonium hydroxide is added dropwise, and under inert gas protection by four-hole boiling flask in oil bath
It is centrifuged after 50-60 DEG C of insulation reaction 18h, and dispersed nano obtained is modified SiO2Particle is stored in ethanol solution,
It forms dispersed nano and is modified SiO2Particle dispersion is for use；
（3）Monodisperse nucleocapsid SiO2The preparation of-PS composite particles：200mL dispersed nanos are modified SiO2Particle dispersion, point
It is dispersed in the 70mL polyvinylpyrrolidone ethanol solutions in four-hole boiling flask, and is added in a manner of being added dropwise under the conditions of nitrogen protection
30mL styrene-azodiisobutyronitrile mixed liquor persistently carries out magnetic agitation, four mouthfuls is heated after magnetic agitation 2-3h at the same time
Mixture is to 65-70 DEG C in flask, and is centrifuged after insulation reaction 12-18h, and by obtained monodisperse nucleocapsid SiO2- PS is multiple
Particle is closed to be stored in ethanol solution；In this step, the polyvinylpyrrolidone ethanol solution is 15g polyvinyl pyrroles
Alkanone K30,65mL ethyl alcohol, the allotment of 15mL deionized waters are made, and the styrene-azodiisobutyronitrile mixed liquor is 20mL's
Styrene is made with the allotment of 1mg azodiisobutyronitriles；
（4）SiO2The preparation of-PS nucleocapsid ceramic diaphragm coating slurries：By monodisperse nucleocapsid SiO2- PS composite particles use
After toluene washing, centrifuges and take monodisperse nucleocapsid SiO2- PS composite particles, aqueous adhesive, solvent are with 70-100:1~5:500~
1000 weight ratio mixing, after ultrasonic disperse 1-2h, magnetic agitation 3-5h makes each component, and fully dispersed to be formed uniformly quality equal
Even mixed serum, slurries obtain SiO after crossing 200 mesh sieve2- PS nucleocapsid ceramic diaphragm coating slurries, in the present embodiment,
Using acrylonitrile multiple copolymer（LA133）As aqueous binders, using 75% alcohol solvent as solvent；
（5）SiO2It is prepared by-PS nucleocapsid ceramic-coated separators：It, will using automatic coating machine with every face thickness for 2-5 μm
SiO2- PS nucleocapsid ceramic diaphragm coating slurry single or double coated on porosity 30%-60%, thicknesses of layers is 10 ~
After 20 μm of spin processes are prepared on PE non-woven fabrics, 12-18h is dried with 55-65 DEG C of vacuum drying oven, obtains SiO2- PS nucleocapsid knots
Structure ceramic coated separator.
Embodiment 2
The present embodiment is on the basis of embodiment 1, in step（4）In, by monodisperse nucleocapsid SiO2- PS composite particles use toluene
Fully after washing, after being centrifuged at a high speed with 8000rpm or more rotating speeds, reuses ethyl alcohol and fully wash monodisperse nucleocapsid SiO2-
PS composite particles, then centrifuge, and by monodisperse nucleocapsid SiO2- PS composite particles, aqueous adhesive, solvent are with 70-100:1
~5:2-3h is carried out at the same time with mechanical agitation using ultrasonic disperse after 500 ~ 1000 weight ratio mixing, keeps each component fully dispersed
It is formed uniformly homogeneous mixed serum；Two procedures are washed by using toluene washing, ethyl alcohol, can effectively remove monodisperse
Nucleocapsid SiO2The free PS in-PS composite particles surface and other impurity can have during subsequently making diaphragm coating slurry
Effect reduces nucleocapsid SiO2Adherency between-PS composite particles effectively improves nucleocapsid SiO2- PS composite particles are in diaphragm coating slurry
In dispersibility.
Embodiment 3
The present embodiment is modified on the basis of embodiment 2, in the step（1）In, by 20mL concentrated ammonia liquors, 100mL second
Alcoholic solution and 15mL ethyl orthosilicates mix simultaneously, and in step（2）Middle 0.8mg gamma-methyl allyl acyloxypropyls trimethoxy
Silane is mixed with 20mL ethyl alcohol, prepares gamma-methyl allyl acyloxypropyl trimethoxysilane ethanol solution；Step（4）In
Using butadiene-styrene rubber（SBR）With carboxymethyl cellulose（CMC）Compound as aqueous binders, using 50% ethyl alcohol as
The compound of solvent, wherein butadiene-styrene rubber and carboxymethyl cellulose is with 2-3:3 ratio mixing compounding, and adjust monodisperse nucleocapsid
SiO2- PS composite particles, aqueous adhesive, solvent weight ratio be 95-100:5-6:800~1000；Step（5）Middle use is more
Hole PE films are as replacement.
Embodiment 4
The present embodiment is modified on the basis of embodiment 2, in the step（1）In, it will be by 20mL concentrated ammonia liquors, 100mL
Ethanol solution and 20mL ethyl orthosilicates mix simultaneously, and in step（2）Middle 0.8mg gamma-methyl allyl acyloxypropyls trimethoxy
Base silane is mixed with 25mL ethyl alcohol, prepares gamma-methyl allyl acyloxypropyl trimethoxysilane ethanol solution；Step（4）Using
It is middle to use acrylonitrile multiple copolymer（LA133）As aqueous binders, using n,N-dimethylacetamide and water with 8:2 ratio
Example configuration n,N-dimethylacetamide solvent, and adjust monodisperse nucleocapsid SiO2- PS composite particles, aqueous adhesive, solvent
Weight ratio is 75-85:4-6:500~750；Step（5）The middle multilayer complex films using PP and PE are as replacement.
The performance test results of the sample of comparative example 1 and embodiment 1-4 such as the following table 1.
Table 1
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not limited by above-described embodiment
System, it is other it is any without departing from the spirit and principles of the present invention made by changes, modifications, substitutions, combinations, simplifications,
Equivalent substitute mode is should be, is included within the scope of the present invention.
Claims (10)
1. a kind of SiO2The preparation method of-PS nucleocapsid ceramic-coated separators, which is characterized in that include the following steps：
（1）Dispersed nano SiO2The preparation of particle：Concentrated ammonia liquor, ethanol solution and ethyl orthosilicate are mixed simultaneously, with St ber
At room temperature, envelope bottleneck is reacted and is centrifuged after stirring 18-24h method, the dispersed nano SiO that will be obtained2Particle is stored in
Ethanol solution forms dispersed nano SiO2Particle dispersion is for use；
（2）Dispersed nano SiO2The modification of particle：With dispersed nano SiO2The ratio of particle and deionized water 0.85-1 mg/mL
Example, by dispersed nano SiO2Particle dispersion is added in the deionized water in four-hole boiling flask, and after ammonium hydroxide is added dropwise, γ-is added
Methyl allyl acyloxypropyl trimethoxysilane ethanol solution, and under inert gas protection by four-hole boiling flask in 50-60 DEG C of guarantor
It is centrifuged after temperature reaction 18-30h, and dispersed nano obtained is modified SiO2Particle is stored in ethanol solution, is formed single
Disperse nano modification SiO2Particle dispersion is for use；
（3）Monodisperse nucleocapsid SiO2The preparation of-PS composite particles：Dispersed nano is modified SiO2Particle dispersion is dispersed in four
In polyvinylpyrrolidone ethanol solution in mouth flask, and styrene-azodiisobutyronitrile is added dropwise under the conditions of nitrogen protection
Mixed liquor simultaneously continues after stirring 2-3h, is kept stirring and is heated to centrifuging after insulation reaction 12-18h under 65-75 DEG C of state,
And by obtained monodisperse nucleocapsid SiO2- PS composite particles are stored in ethanol solution；
（4）SiO2The preparation of-PS nucleocapsid ceramic diaphragm coating slurries：By monodisperse nucleocapsid SiO2- PS composite particles use first
After benzene washing, centrifuges and take monodisperse nucleocapsid SiO2- PS composite particles, aqueous adhesive, solvent are with 70-100:1~5:500~
1000 weight ratio mixing makes each component is fully dispersed to be formed uniformly homogeneous mixed serum, and slurries obtain after crossing 200 mesh sieve
Obtain SiO2- PS nucleocapsid ceramic diaphragm coating slurries；
（5）SiO2It is prepared by-PS nucleocapsid ceramic-coated separators：Using automatic coating machine by SiO2- PS nucleocapsid ceramic diaphragms
After coating slurry single or double is coated on polyolefin porous separator, 12-18h is dried with 55-65 DEG C of vacuum drying oven, is made
SiO2- PS nucleocapsid ceramic-coated separators.
2. SiO as described in claim 12The preparation method of-PS nucleocapsid ceramic-coated separators, which is characterized in that the step
（1）In, the volume ratio of the concentrated ammonia liquor, ethanol solution and ethyl orthosilicate is 1 ~ 2:5~15:1~2；After centrifugation, sieve takes grain
Diameter is in 50 nm and dispersed nano SiO below2Particle is stored in ethanol solution for use.
3. SiO as described in claim 12The preparation method of-PS nucleocapsid ceramic-coated separators, which is characterized in that the step
（2）In, the gamma-methyl allyl acyloxypropyl trimethoxysilane ethanol solution concentration is 0.02-0.05mg/mL；Deionization
Water:The volume ratio of gamma-methyl allyl acyloxypropyl trimethoxysilane ethanol solution is 2-5:1.
4. SiO as described in claim 12The preparation method of-PS nucleocapsid ceramic-coated separators, which is characterized in that the step
（3）In, the polyvinylpyrrolidone ethanol solution is the ethanol solution of PVP K30 and 50%-75% with 0.2-
0.5mg/mL allotments are made, and the styrene-azodiisobutyronitrile mixed liquor is azodiisobutyronitrile with 0.02-0.05mg/
ML concentration is dissolved in styrene allotment and is made, and dispersed nano is modified SiO2Particle dispersion：Polyvinylpyrrolidone ethyl alcohol is molten
The total volume ratio of liquid, styrene-azodiisobutyronitrile mixed liquor is 2-3:1.
5. SiO as described in claim 12The preparation method of-PS nucleocapsid ceramic-coated separators, which is characterized in that the step
（4）In, by monodisperse nucleocapsid SiO2After-PS composite particles are centrifuged at a high speed after fully being washed using toluene, filled using ethyl alcohol
Divide washing monodisperse nucleocapsid SiO2- PS composite particles, then centrifuge and by monodisperse nucleocapsid SiO2It is-PS composite particles, aqueous viscous
Jelly, solvent are with 70-100:1~5:2- is carried out at the same time with mechanical agitation using ultrasonic disperse after 500 ~ 1000 weight ratio mixing
3h makes each component is fully dispersed to be formed uniformly homogeneous mixed serum.
6. SiO as claimed in claim 52The preparation method of-PS nucleocapsid ceramic-coated separators, which is characterized in that the water
Property binder select butadiene-styrene rubber and carboxymethyl cellulose compound, polyvinyl alcohol polyacrylate, gelatin, styrene sulfonic acid
Any one in sodium, acrylonitrile multiple copolymer, dextrin, poly- lithium -4- styrene etc. or compounding.
7. SiO as claimed in claim 52The preparation method of-PS nucleocapsid ceramic-coated separators, which is characterized in that described molten
Agent is ethanol water, water/n,N-dimethylacetamide mixed solvent etc., and the requirement that proportioning can refer to final products is adjusted
It is whole.
8. SiO as described in claim 12The preparation method of-PS nucleocapsid ceramic-coated separators, which is characterized in that the step
（5）In, the polyolefin porous separator is the PP films of porosity 30%-60%, PE films, PP and PE multilayer complex films, passes through spinning
Any one in non-woven polyolefin prepared by silk method, the thicknesses of layers of the polyolefin porous separator is 10-20 μm, per side
SiO22-5 μm of-PS nucleocapsid ceramic diaphragm coating slurries coating layer thickness.
9. a kind of SiO prepared by any one of claim 1~8 the method2- PS nucleocapsid ceramic-coated separators.
10. SiO as claimed in claim 92Application of-PS nucleocapsid the ceramic-coated separators in lithium ion battery separator.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810689956.5A CN108735953B (en) | 2018-06-28 | 2018-06-28 | SiO (silicon dioxide)2-PS core-shell structure ceramic coating diaphragm and preparation method and application thereof |
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| CN109985584A (en) * | 2019-04-23 | 2019-07-09 | 河北工业大学 | A kind of preparation method of regulatable strawberry shape silica-organic hybrid complex microsphere |
| CN111081944A (en) * | 2019-12-18 | 2020-04-28 | 江苏厚生新能源科技有限公司 | Multilayer microporous composite polyolefin membrane, preparation method thereof, lithium ion battery and FE racing car |
| CN111244362A (en) * | 2020-01-15 | 2020-06-05 | 惠州锂威新能源科技有限公司 | Composite diaphragm, preparation method thereof and lithium ion battery |
| CN111560238A (en) * | 2020-05-07 | 2020-08-21 | 库尔勒明洋工贸有限责任公司 | Environment-friendly drilling fluid lubricant and preparation method thereof |
| CN111883721A (en) * | 2020-07-01 | 2020-11-03 | 湖南翰墨新材料有限公司 | Inorganic nano polymer modified polyolefin lithium battery diaphragm and preparation method thereof |
| CN112582749A (en) * | 2020-12-11 | 2021-03-30 | 重庆金美新材料科技有限公司 | Safe lithium ion battery diaphragm, preparation method and lithium ion battery |
| CN113381123A (en) * | 2021-06-29 | 2021-09-10 | 中海油天津化工研究设计院有限公司 | SiO (silicon dioxide)2Method for modifying meta-aramid lithium ion battery diaphragm by using nano particles |
| CN115832623A (en) * | 2022-10-14 | 2023-03-21 | 宁德时代新能源科技股份有限公司 | Separator, method for producing same, secondary battery, and power-using device |
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| CN109985584A (en) * | 2019-04-23 | 2019-07-09 | 河北工业大学 | A kind of preparation method of regulatable strawberry shape silica-organic hybrid complex microsphere |
| CN109985584B (en) * | 2019-04-23 | 2021-09-21 | 河北工业大学 | Preparation method of adjustable and controllable strawberry-shaped silicon dioxide-organic hybrid composite microspheres |
| CN111081944A (en) * | 2019-12-18 | 2020-04-28 | 江苏厚生新能源科技有限公司 | Multilayer microporous composite polyolefin membrane, preparation method thereof, lithium ion battery and FE racing car |
| CN111081944B (en) * | 2019-12-18 | 2021-04-13 | 江苏厚生新能源科技有限公司 | Multilayer microporous composite polyolefin membrane, preparation method thereof, lithium ion battery and FE racing car |
| CN111244362A (en) * | 2020-01-15 | 2020-06-05 | 惠州锂威新能源科技有限公司 | Composite diaphragm, preparation method thereof and lithium ion battery |
| CN111244362B (en) * | 2020-01-15 | 2022-09-30 | 惠州锂威新能源科技有限公司 | Composite diaphragm, preparation method thereof and lithium ion battery |
| CN111560238A (en) * | 2020-05-07 | 2020-08-21 | 库尔勒明洋工贸有限责任公司 | Environment-friendly drilling fluid lubricant and preparation method thereof |
| CN111560238B (en) * | 2020-05-07 | 2021-02-19 | 库尔勒明洋工贸有限责任公司 | Environment-friendly drilling fluid lubricant and preparation method thereof |
| CN111883721A (en) * | 2020-07-01 | 2020-11-03 | 湖南翰墨新材料有限公司 | Inorganic nano polymer modified polyolefin lithium battery diaphragm and preparation method thereof |
| CN112582749A (en) * | 2020-12-11 | 2021-03-30 | 重庆金美新材料科技有限公司 | Safe lithium ion battery diaphragm, preparation method and lithium ion battery |
| CN113381123A (en) * | 2021-06-29 | 2021-09-10 | 中海油天津化工研究设计院有限公司 | SiO (silicon dioxide)2Method for modifying meta-aramid lithium ion battery diaphragm by using nano particles |
| CN115832623A (en) * | 2022-10-14 | 2023-03-21 | 宁德时代新能源科技股份有限公司 | Separator, method for producing same, secondary battery, and power-using device |
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Effective date of registration: 20220106 Address after: 230000 intersection of Jianling road and Cuihu 4th Road, Tongling Economic Development Zone, Anhui Province Patentee after: Anhui Meixin New Material Co.,Ltd. Address before: 515000 1st floor, film blowing workshop, no.1/288, Fudi Road, Jinping District, Shantou City, Guangdong Province Patentee before: GUANGDONG MEILIAN DIAPHRAGM Co.,Ltd. |